Use of single wall carbon nanohorns in polymeric electrolyte fuel cells

Single wall carbon nanohorns (SWNH), produced by AC arc discharge in air, were used as Pt and PtRu supports in polymer electrolyte membrane fuel cells (PEMFC). These electrocatalysts were compared with equivalent electrocatalysts supported on commercial carbon back. The SWNH were characterized by differential thermal analysis (DTA), TEM, SEM, and XRD. The produced SWNH were 84.5 wt% pure, containing 3 wt% of amorphous carbon and 12.5 wt% of graphitic carbon. SWNH were used as electrocatalyst supports and tested in the electrodes of two types of polymer electrolyte fuel cells: H₂-fed PEMFC and direct methanol fuel cells (DMFC). The electrocatalyst nanoparticles anchored on both carbon supports were ca. 2.5 nm in diameter obtained by employing ethylene glycol as the reducing agent. The use of SWNH showed catalytic activities 60% higher than using carbon black as the electrocatalyst support in both types of fuel cells.     

Plasma-polymerised electrolyte membrane for miniaturised direct methanol fuel cells

This article looks at the development of thin-film electrolyte membranes, which can be combined with thin-film porous graphite electrodes to form a membrane electrode assembly for fuel cells. In particular, details are given of a miniaturised direct methanol fuel cell, based on the use of micro-system technologies, including the thin-film membrane assembly.     

Cathodoluminescence of TiO2 nanotubes prepared by low-temperature anodization of Ti foils

We show that anodization of Ti sheets in an ethylene glycol and HF containing electrolyte at temperatures under 0 °C results in the formation of a self-arranged ordered porous structure at the top surface of the sample. This perforated surface structure initiates the growth of an ordered array of titania nanotubes. The inner diameter of nanotubes can be modified in a controlled fashion in the range from 10 nm to more than 250 nm through the change of the electrolyte temperature from −20 °C to + 50 °C. The spectral distribution of cathodoluminescence from a cluster of nanotubes clearly demonstrates the formation of resonator modes which are separated from each other by around 200 meV.     

铜纳米线阵列的模板组装

采用电解法溶解多孔阳极氧化铝(PAA)模板的阻挡层,用直流电沉积的方法在模板中组装了铜纳米线阵列.分别用扫描电镜和X射线衍射表征铜纳米线阵列的形貌和晶体结构,用电化学法表征了铜纳米线阵列的电催化性能.结果表明,PAA去阻挡层后,伏安图上出现一个阳极氧化峰.恒电位沉积的铜纳米线直径为22nm,沿(111)晶面择优取向.铜纳米线阵列电极能催化亚硝酸根的还原,其催化电流比本体铜电极上大2倍,峰电位正移80mV.纳米铜阵列电极可用于亚硝酸盐的电化学检测.     

氧化锆多孔膜和致密膜制备方法研究进展

氧化锆膜表面性质特殊,耐腐蚀和耐高温性能优异,具有良好的开发价值和应用前景．作者对氧化锆多孔陶瓷膜（平均孔径为２～１００ｎｍ）及氧化锆致密膜的制备方法进行了综述．     

Engineering porous materials for fuel cell applications

Porous materials play an important role in fuel cell engineering. For example, they are used to support delicate electrolyte membranes, where mechanical integrity and effective diffusivity to fuel gases is critical; they are used as gas diffusion layers, where electronic conductivity and permeability to both gas and water is critical; and they are used to construct fuel cell electrodes, where an optimum combination of ionic conductivity, electronic conductivity, porosity and catalyst distribution is critical. The paper will discuss these characteristics, and introduce the materials and processing methods used to engineer porous materials within two of the leading fuel cell variants, the solid oxide fuel cell and the polymer electrolyte membrane fuel cell.     

Fabrication of sub-25 nm diameter pillar nanoimprint molds with smooth sidewalls using self-perfection by liquefaction and reactive ion etching

Self-perfection by liquefaction (SPEL) was used to fabricate nanoimprint molds with an array of sub-25?nm diameter pillars (200?nm period), resulting in nearly perfect cylindrical shape and smooth sidewalls. SPEL turned an array of irregularly shaped Cr polygons into an array of nearly perfect circular dots with small diameter. The Cr dot arrays were then transferred to SiO(2) or Si pillar arrays by means of reactive ion etching to produce imprint molds. High-fidelity nanoimprint lithography using the pillar molds was also demonstrated.     

Electrochemical Fabrication of Metallic Nanowires and Metal Oxide Nanopores

A nuclear track etched polycarbonate membrane filter with numerous cylindrical nanopores was applied as a nanoporous template for growing metallic nanowires. Nickel, cobalt, and iron nanowires were electrodeposited into the cylindrical nanopores. Cathodic polarization curves were measured to determine an optimum condition for growing nanowires. The shape of nanowires was observed using scanning electron microscope (SEM) and the crystal structure was analyzed using transmission electron microscopy (TEM). Diameter and length of nanowires corresponded to those of nanopores and each nanowire was composed of a single crystal. Anodized aluminum oxide films were also fabricated as a novel nanoporous template. The pore length and diameter was controlled changing anodizing conditions. Ordering behavior of nanopores array in an anodized aluminum oxide film was also investigated to make a novel nanoporous template with a highly ordered honeycomb array of nanopores.     

Supported and unsupported platinum catalysts prepared by a one-step dry deposition method and their oxygen reduction reactivity in acidic media

The present study examines the physical and electrochemical properties of platinum particles generated by a combustion method for use in oxygen reduction on the cathode side of a proton exchange fuel cell (PEMFC). This method employs a one-step, open-atmosphere, and dry deposition technique called reactive spray deposition technology (RSDT). The objective of this study is to characterize the intrinsic activity of the platinum produced for incorporation into low-loading cathode electrodes in high performing membrane electrode assemblies (MEA). The process allows for independent real-time control of the carbon, platinum, and ionomer ratios in the final electrode. In this research work we examine the oxygen reduction reaction via a rotating disk three electrode set-up to understand the intrinsic activity of the as-sprayed platinum as well as platinum condensed onto a carbon support. The mass and specific activities were measured in a 0.1 M perchloric acid electrolyte under different deposition conditions and loading was verified by atomic emission spectroscopy inductively coupled plasma (AES-ICP). Microscopy results indicate that the platinum particle sizes are 5 nm (σ = 2.8 nm) in diameter while TEM and XRD show that the platinum generated by the process is pure and crystalline without bulk oxides or precursor material present. The initial rotating disk electrode result shows that the RSDT technique is capable of producing catalysts with an oxygen reduction mass activity at 0.9 V of 200 mA/mg_Pt rotating at 1600 rpm and 30 °C. The electrochemically active surface area approaches 120 m²/g for the platinum, carbon, and ionomer samples and the unsupported sample with only platinum has an active area of 92 m²/g. The rather larger surface area of the unsupported sample exists when the platinum is deposited as a highly porous nanostructured layer that allows for high penetration of reactant.     

Spatially resolved, in situ potential measurements through porous electrodes as applied to fuel cells

We report the development and use of a microstructured electrode scaffold (MES) to make spatially resolved, in situ, electrolyte potential measurements through the thickness of a polymer electrolyte fuel cell (PEFC) electrode. This new approach uses a microfabricated apparatus to analyze the coupled transport and electrochemical phenomena in porous electrodes at the microscale. In this study, the MES allows the fuel cell to run under near-standard operating conditions, while providing electrolyte potential measurements at discrete distances through the electrode's thickness. Here we use spatial distributions of electrolyte potential to evaluate the effects of Ohmic and mass transport resistances on the through-plane reaction distribution for various operating conditions. Additionally, we use the potential distributions to estimate the ionic conductivity of the electrode. Our results indicate the in situ conductivity is higher than typically estimated for PEFC electrodes based on bulk polymer electrolyte membrane (PEM) conductivity.     

Electrochemical synthesis of antimony nanowires and analysis of diffusion layers

Synthesis of an array of antimony nanowires was performed by electrodeposition within a porous polycarbonate membrane. The sizes of pores range from 30 to 400 nm in diameter and their densities vary from 2 x 10(+6) to 2 x 10(+9) pores/cm2. To obtain optimal conditions for nanowire preparation, plating behavior was investigated by a potentiostatic method with two types (continued or pulsed) of polarization. The chronoamperometry revealed that responses depend on the type of polarization and on the pore density of the membrane. With high-density membranes, the diffusion layers of each individual pore immediately overlap when they reach the external part of the membrane. This leads to an abrupt decrease of current intensity. This phenomenon is not observed with low-density membranes because of the greater distance between pores. This mechanism, which was investigated in antimony nanowire plating, is applicable to electrodeposition of other types of materials.     

Preparation and magnetic properties of cylindrical NiFe films and antidot arrays

Continuous NiFe (Permalloy) cylindrical films and arrays of cylindrical NiFe antidots 7 nm thick have been prepared by sputtering onto cylindrical aluminum wires and onto wires anodized to form a porous anodic alumina layer. The antidots are arranged in a close-packed pattern determined by the hexagonal pore arrangement in the porous alumina, with period 103 nm and diameter 42 nm. Hysteresis loops were measured at different angles with respect to the cylinder axis and indicate an easy plane normal to the radius of the wire. The antidots enhance the coercivity compared to the continuous cylindrical film.     

Variation of nanopore diameter along porous anodic alumina channels by multi-step anodization

In order to form tapered nanocapillaries, we investigated a method to vary the nanopore diameter along the porous anodic alumina (PAA) channels using multi-step anodization. By anodizing the aluminum in either single acid (H3PO4) or multi-acid (H2SO4, oxalic acid and H3PO4) with increasing or decreasing voltage, the diameter of the nanopore along the PAA channel can be varied systematically corresponding to the applied voltages. The pore size along the channel can be enlarged or shrunken in the range of 20 nm to 200 nm. Structural engineering of the template along the film growth direction can be achieved by deliberately designing a suitable voltage and electrolyte together with anodization time.     

静电纺丝制备多孔醋酸纤维素超细纤维

采用静电纺丝法制备了大量尺寸为60 nm～750 nm椭圆形多孔醋酸纤维素(CA)纤维.利用扫描电镜(SEM)表征了纤维及孔的形态和大小,液氮吸附法(BET)测定了纤维的比表面积.探讨了溶刑种类、溶剂配比和溶液浓度对多孔CA纤维的影响.通过调节纺丝溶液性质和纺丝参数,CA纤维表面多孔大小和分布密度是可调控的.成孔机理是...     

Thermodynamic modeling of power plants based on solid oxide fuel cells

A mathematical model of a solid oxide fuel cell is presented for investigation of the thermodynamic cycles of power plants. The model is one-dimensional in two directions: in the direction of fuel flow in the supply channel and perpendicular to the contact planes of the electrolyte and electrodes. Electrochemical reactions are assumed to run in the area of nonzero width adjoining the electrolyte. Natural gas is taken as a fuel, and its internal steam conversion in a porous anode is considered. Heat transfers are governed by the model of a generalized heat exchanger, described by accumulation curves of temperature-versus-power for heat sources and sinks. A binary plant with a fuel cell at atmospheric pressure and a subatmospheric gas-turbine bottoming is considered as an example.     

Nano-holes in silicon wafers using laser-induced surface plasmon polaritons

Surface Plasmon Polaritons (SPPs) have been explored for a multitude of applications including sub-wavelength lithography, data storage, microscopy and photonics. In this paper, we report the use of SPPs for nanomachining silicon in massively parallel fashion. A Q-switched Nd:YAG laser beam was impinged on gold-thin film deposited, porous alumina membrane (PAM) that contains periodic 2-D array of thousands of nano-holes. The silicon substrate was placed in close proximity with PAM. The formation of SPPs and their coherent interference at the exit of PAM holes created strong nanoscale electrical fields which in turn produced 50-70 nm diameter holes in silicon.     

Ultrasound attenuation in cylindrical micro-pores: Nondestructive porometry of ion-track membranes

The propagation of ultrasonic waves in the cylindrical micro-pores (pore diam. <1 μm) of ion-track membranes (ITMs) is studied. This membrane fabrication technique provides unique possibilities to obtain cylindrical micro-pores with a very high degree of accuracy in pore shape, size, and orientation. Several ITMs were specially produced having the same pore diameter, orientation, and geometry, but different thickness. Porosity, pore diameter, and shape were determined using scanning electron microscopy, and then the coefficient of ultrasound transmission was measured using air coupling and spectral analysis. These experimental conditions permit us to eliminate the influence of the boundary conditions and to achieve a strong decoupling between the fluid filling the pores and the solid constituent of the membrane. Hence, the velocity and the attenuation coefficient for ultrasound propagation in the pores can be measured. These parameters are compared with the predictions made by conventional theories for sound propagation in porous media and in cylindrical channels. The conclusions of this work provide a better understanding of wave propagation in micro-pores and establish the basis of an ultrasonic porometry technique for ITMs.     

Addressable nanoelectrode membrane arrays: fabrication and steady-state behavior

An addressable nanoelectrode membrane array (ANEMA) based on a Au-filled track-etched polycarbonate membrane was fabricated. The Au-filled membrane was secured to a lithographically fabricated addressable ultramicroelectrode (UME) array patterned with 25 regularly spaced (100 microm center to center spacing), 10 microm diameter recessed Pt UMEs to create 25 microregions of 10 microm diameter nanoelectrode ensembles (NEEs) on the membrane. The steady-state voltammetric behavior of 1.0 mM Ru(NH(3))(6)Cl(3) and 1.0 mM ferrocene methanol in 0.1 M KCl on each of the micro NEEs resulted in sigmoidal-shaped voltammograms which were reproducible across the ANEMA. This reproducibility of the steady-state current was attributed to the overlapping hemispherical diffusion layers at the Au-filled nanopores of each 10 microm diameter NEE of a ANEMA. The track-etched polycarbonate membranes were filled using a gold electroless deposition procedure into the 30 nm diameter pores in the membrane. Electrical connection between the Au-filled template array and the lithographic UME platform array was achieved by potentiostatic electrodeposition of Cu from an acidic copper solution into each of the 25 recessed Pt UMEs on the UME array platform. A multiplexer unit capable of addressing 64 individual micro NEEs on an ANEMA is described. ANEMAs have advantages of high reproducibility, facile fabrication, multitime reuse of lithographically fabricated UME arrays, and purely steady-state behavior.     

Nanoporous materials: Porous Graphene as an Atmospheric Nanofilter (Small 20/2010)

The fabrication of nanoscale membranes exhibiting high selectivity is an emerging field of research. The possibility to use bottom‐up approaches to fabricate a filter with porous graphene and analyze its functionality with first principle calculations is investigated. Here, the porous network is produced by self‐assembly of the hexaiodo‐substituted macrocycle cyclohexa‐m‐phenylene (CHP). The resulting porous network exhibits an extremely high selectivity in favor of H₂ and He among other atmospheric gases, such as Ne, O₂, N₂, CO, CO₂, NH₃, and Ar. The presented membrane is superior to traditional filters using polymers or silica and could have great potential for further technological applications such as gas sensors or fuel cells.     

冷滚法制备熔融碳酸盐燃料电池用LiAlO2隔膜

以水作溶剂，采用冷滚法制备熔融碳酸盐燃料电池用ＬｉＡｌＯ２隔膜，这种方法不使用有机毒性溶剂，不污染环境，工艺简便，成本低，制得的隔膜厚度薄，孔分布均匀，易浸入及保持电解质，可以耐受一定范围内的电池组装压力变化和电池多次启动冷热冲击，电池性能不变，依旧保持良好。